Microbicidal agents containing as active ingredient monohydroxyphenyl carbinols

ABSTRACT

Monohydroxyphenyl carbinols with at least two halogen atoms in the molecule have been found as microbicides which are effective against various types of bacteria and fungi.

This is a division of application Ser. No. 553,350 filed on Feb. 26, 1975, now U.S. Pat. No. 3,944,652, which is a division of application Ser. No. 164,446 filed on July 20, 1971, now U.S. Pat. No. 3,879,477.

This invention relates to monohydroxyphenyl carbinols, their manufacture and use.

According to the present invention there are provided monohydroxyphenyl carbinols of the general formula ##STR1## wherein X is halogen,

X₁, x₂ and X₃ are each halogen or hydrogen, and

R is a straight or branched chain alkyl group of 1-8 carbon atoms, or cycloalkyl group of 3-8 carbon atoms or phenyl, unsubstituted or substituted by halogen and/or alkyl of 1-2 carbon atoms, there being at least 2 halogen atoms in the molecule.

These compounds possess microbicidal activity.

The hydroxyl group in formula I is preferably in 2- or 4- position. The most important cycloalkyl groups are cyclopentyl and, especially, cycloheryl.

The alkyl groups can be, for example, methyl, ethyl and all isomers of propyl, butyl, amyl, hexyl, heptyl and octyl. Halogen includes bromine and chlorine.

Formula I includes hydroxyphenyl carbinols of the formula ##STR2## wherein X, X₁, X₂ and X₃ have the meanings given above, and Y and Y₁ are each methyl, halogen or hydrogen. Y₂, Y₃ and Y₄ are each halogen or hydrogen, there being at least 2 halogen atoms in the formula, and the phenolic hydroxy group being in the 2- or 4-position to the carbinol bridge, as well as hydroxyphenyl alkyl carbinols of the formula ##STR3## WHEREIN X' is halogen and Alk is straight or branched chain alkyl of 1-8 carbon atoms, and X, X₁ and X₂ have the meaning given above, wherein the hydroxy group is in 2- or 4-position to the carbinol bridge.

In the compounds of formula 2 there are generally never more than 6 halogen atoms.

Among the compounds of formula 3, the 2-hydroxyphenyl derivatives are particularly notable. Preferred alkyl groups have 3-7 carbon atoms, these groups being preferably unbranched.

Particularly interesting microbicidal are those 2-hydroxyphenyl alkyl carbinols of formula 3 wherein X and X' are the same and are chlorine or bromine, while X₁ and X₂ are hydrogen and Alk is n-butyl or n-amyl.

Furthermore, of great particular interest are monohydroxybenzhydrols of the formula ##STR4## wherein X, X₁, X₂, X₃, Y, Y₂ and Y₃ have the meanings given above and wherein at least two of X₁, X₂, X₃, Y, Y₂ and Y₃ are different from hydrogen.

Within the scope of formula 4 are compounds of particular interest and of the formula ##STR5## wherein n is 2,3 or 4, and m is 1, 2 or 3, and n + m is 3, 4 or 5.

The most important 4-hydroxybenzhydrols are given by the formula ##STR6## wherein p and q are each 1, 2 or 3 and p + q is 3 or 4.

In order to manufacture the monohydroxphenyl carbinols of the invention, a ketone of the formula ##STR7## wherein X, X₁, X₂, X₃ and R have the meanings given above is reduced. The compounds of formulae 2 to 6 can be made from ketones of the formula ##STR8## wherein the various symbols have the meanings given above, and the numbers of substituents and position of the hydroxy group are as given above also.

As reducing agent, for example a hydride can be used, the reaction being carried out in a solvent medium inert to the hydride.

For this, sodium borohydride is used with advantage, generally 0.25 - 1 mol per mol of the hydroxyphenyl ketone to be reduced, corresponding to 1 to 4 equivalents. Particularly good yields are obtained if a polar solvent is used such as water, methanol, ethanol, isopropanol or dioxane, or mixtures of these solvents such as a water/methanol mix. The hydroxyphenyl ketone to be reduced is generally subjected to reaction in the form of a phenolate, i.e. in salt form, preferably an alkali salt such as the ammonium, potassium or, particularly the sodium salt.

The reaction temperature may vary for example between 0° C and the boiling temperature of the solvent used. The reaction time is correspondingly generally 20 to 1 hours.

Further reduction methods which can be used are reduction with zinc dust in alcoholic alkali hydroxide solution, for example potassium hydroxide or sodium hydroxide, and reduction by means of sodium amalgam in alcoholic solution or by means of aluminium isopropylate in isopropanolic solution ( the method of Meerwein-Ponndorf-Verley).

Note should also be taken of the catalytic hydrogenation of hydroxyphenyl ketones to give the hydroxyphenyl carbinols of the present invention.

The hydroxyphenyl ketones used as starting products are known (see Belgian Patent Specifications 753,533 and 753,534) or are manufactured by methods known per se, for example from the corresponding benzoic acid or alkane carboxylic acid phenyl esters by the Fries reaction (compare "Baltzly et al. Journal of the American Chemical Society 77, 2522 (1955)", "L.F. and M. Fieser, Lehrbuch der organischen Chemie 1954, page 728" or "G.A. Olah, Friedel-Crafts and Related Reactions 1964, page 499"). The reaction can take place in the molten state or in the presence of an organic solvent medium, e.g. nitrobenzene. On heating the corresponding phenyl ester together with aluminium chloride there results the monohydroxybenzophenone or monohydroxyphenylalkyl ketone.

Particularly surprising for the compounds according to the invention is the broad spectrum of anti-bacterial activity, which for most of the compounds extends both over the area of gram-positive and gram-negative bacteria. From an application point of view, the lack of smell and the colourlessness of the compounds of the invention is of particular value.

The present invention includes quite generally the use of the compounds according to the invention in pest combating. The use of the anti-microbial compounds is possible on a very wide basis, particularly for the protection of organic substrates against attack by destructive and pathogenic micro organisms (including phytopathogenic ones). The anti-microbial agents noted are also suitable both as a preserving agent and as a disinfectant for technical products of all types, for plant protection, in farming, in veterinary medicines and in cosmetic technology.

The monohydroxybenzhydrols according to the invention are thus used for treating or protecting organic materials, particularly textiles, by impregnating at least one of these compounds into the material to be treated or protected or by applying such to the surface of the materials.

Among non-textile technical products which can be preserved with the aid of compounds according to the invention, the following examples should be noted:

Glues, binding agents, coating agents, textile dressings and treating agents, printing and colouring pastes and similar preparations on the basis of organic and inorganic dyes or pigments, also those which contain in admixture casein or other organic compounds. Also wall and ceiling coatings, e.g. such as have an albumen containing colour binding agent, are protected by addition of a compound according to the invention from attack by pests. Use for wood protection is likewise possible.

In the cellulose and paper industry also, the compounds according to the invention can be used as conservation agents, inter alia for preventing the known slime formation generated by micro organisms infestation in the apparatus and machinery used for papermaking.

Furthermore by combination of the monohydroxybenzhydrols of the invention with surface active agents, particularly washing active agents it is possible to produce washing and cleaning agents with exceptional anti-bacterial or anti-mycotic action. The compounds according to the invention can, for example, be blended into soaps or combined with soap-free washing agents or other surface active materials, particularly non-ionic and cationic washing agents, or they can be combined together with mixtures of soaps and soap-free washing materials, wherein in these combinations their anti-microbial effectiveness is retained to the fullest degree. By the use of aqueous preparations of such washing and cleaning agents containing monohydroxybenzhydrols according to the invention, textile materials, for example, can be treated anti-microbially during washing, since the active agent is substantive to the textile material.

Cleaning agents which contain the compounds of the above noted formulae can be used both in industrial and domestic use, also in foodstuff industries e.g. dairies, breweries and slaughter houses. The present compounds can also be used as a component of preparations which are used for cleaning or disinfection.

The action of the monohydroxybenzhydrols according to the invention can also be used in conserving and disinfecting preparations for plastics materials. In the use of plasticisers it is advantageous to add the anti-microbial addition to the plastics material dissolved or dispersed in the plasticiser. It is advisable to take pains to obtain as even as possible a distribution in the plastics material. The plastics materials with anti-microbial properties can be used for useful articles of all types in which an effectiveness against varied germs, e.g. bacteria and fungi, is desired, thus for example in foot mats, bath curtainings, seats, steps in swimming baths, wall coverings, etc. By incorporation into suitable waxing and polishing compositions, suitable floor cleaning and furniture care materials with disinfectant action can be produced.

Furthermore the compounds according to the invention can be used for the conserving and disinfecting treatment of fibres and textiles, wherein they can be applied to both natural and synthetic fibres and there effect a permanent action against harmful (and pathogenic) micro organisms, for example fungi and bacteria. The addition of these compounds can take place therein before simultaneously with or after the treatment of these textiles with other materials e.g. printing or dyeing pastes, dressings, etc.

Textiles treated in this way also are protected against the generation of a sweaty smell as is generated by micro organisms.

Treatment can take place for example by impregnating or spraying with solutions or suspensions containing the above noted compounds as active agent. The active agent can vary according to the purpose of use between 0.1 and 50 grams active substance per litre, preferably 1 - 30 grams.

Generally textile materials of both synthetic or natural origin can be satisfactorily protected against attack by mould fungi or bacteria by a content of from 0.1 to 3% of active agent. The active agent noted can be added together with other textile treatment agents as dressing agents, permanent creasing treatments etc.

The ways of using the active agents of the present invention can correspond to the usual formulations for pest control agents, for example, agents which contain the said active agent can optionally also contain additives such as solvents, dispersing agents, wetting agents, adhesives, light protection agents, optical brighteners etc., together with other pest control agents, such as fungicides and bactericides. Particularly, however, as well as the active agent according to the invention, the agent can contain a further solid or liquid thinning agent or a solid or liquid carrier. The invention extends to microbicidal agents which contain compounds of the general formula I.

The following examples will serve to illustrate the invention.

EXAMPLE 1

A. To a solution of 1.2 grams sodiumhydroxide in 10 ml water and 50 ml methanol there was added 9.0 g 2-hydroxy-5,3',4'-trichlorobenzophenone and 0.6 g sodiumborohydride. The reaction solution was kept for 5 hours at 25° C with stirring. After addition of 50 ml 2-n-hydrochloric acid the product was extracted with ethyl acetate and the extract washed first with saturated potassium bicarbonate solution and then with water. The extract dried over sodium sulphate left behind 8.6 g of the compound of formula ##STR9## which was an oil which crystallised on standing; melting point 120°-128° C.

The purified compound from recrystallisation from chloroform melted at 130°-131° C. The pure yield amounted to 7.3 g.

B. To 31 g aluminiumisopropylate in 150 ml isopropanol there was added a solution of 9.0 g 2-hydroxy-5,3',4'-trichlorobenzophenone in 25 ml isopropanol. The reaction mixture was then boiled under reflux for 20 hours. After the addition of 150 ml 2-n-hydrochloric acid at 25° C, the product was extracted with ethyl acetate and the extract washed first with saturated potassium bicarbonate solution and then with water. From the extract which was dried over sodium sulphate there remained after the removal of the solvent 8.5 g of the compound 100 as an oil which crystallised on standing.

After recrystallisation from chloroform the compound was present in pure form and melted at 130°-131° C.

In the same way as example 1 or according to one of the other methods given above the following compounds can be prepared which are shown in the following table A: ##STR10##

                  TABLE A                                                          ______________________________________                                         Com-                                              Melting                      pound                                             point in                     No.   R.sub.1                                                                               R.sub.2                                                                              R.sub.3                                                                             R.sub.4                                                                            R.sub.5                                                                            R.sub.6                                                                             R.sub.7                                                                             R.sub.8                                                                            R.sub.9                                                                            ° C                   ______________________________________                                         100   OH     H     H    Cl  H   H    Cl   Cl  H   131- 132                     101   OH     H     H    Cl  H   H    Cl   H   H   102-104                      102   OH     H     Cl   H   H   H    Cl   H   Cl  < 30                         103   OH     Cl    H    Cl  H   H    Cl   Cl  H   155-157                      104   OH     H     H    Cl  H   H    Cl   H   Cl  110-112                      105   OH     Cl    H    Cl  H   H    Cl   H   H   93-94                        106   OH     Cl    H    Cl  H   H    Cl   H   Cl  106-107                      107   OH     Cl    H    Cl  Cl  H    Cl   H   Cl  133-134                      108   OH     Cl    H    Cl  Cl  H    Cl   H   H   176-178                      109   OH     H     Cl   H   Cl  H    Cl   Cl  H   145-146                      110   OH     H     Cl   H   H   H    Cl   Cl  H   106-107                      111   OH     Cl    H    Cl  Cl  H    Cl   Cl  H   189-190                      112   OH     H     H    Cl  Cl  H    Cl   Cl  H   Oil                          113   OH     H     H    Br  H   H    Cl   Cl  H   134-135                      114   OH     Br    H    Br  H   H    Cl   Cl  H   124-125                      115   OH     H     Cl   H   Cl  Cl   Cl   H   H   135-136                      116   OH     H     Cl   Cl  H   Cl   Cl   H   H   119-120                      117   OH     H     H    Br  H   Cl   Cl   H   H   103-104                      118   OH     Br    H    Br  H   Cl   Cl   H   H   278-279                      119   OH     H     Cl   H   Cl  Cl   H    Cl  H   146-147                      120   OH     H     Cl   H   H   Cl   H    Cl  H   135-136                      121   OH     Cl    H    Cl  Cl  Cl   H    Cl  H   156-157                      122   OH     H     Cl   Cl  H   Cl   H    Cl  H   182-183                      123   OH     H     Cl   H   Cl  Cl   H    H   Cl  175-176                      124   OH     Cl    H    Cl  Cl  Cl   H    H   Cl  189-190                      125   OH     H     Cl   Cl  H   Cl   H    H   Cl  156-157                      126   OH     H     Cl   Cl  H   H    Cl   H   H   98-99                        127   OH     H     Cl   H   Cl  CH.sub.3                                                                            H    H   H   115-116                      128   OH     H     Cl   H   H   CH.sub.3                                                                            H    H   H   131-132                      129   OH     Cl    H    Cl  Cl  CH.sub.3                                                                            H    H   H   153-154                      130   OH     H     Cl   H   Cl  Cl   H    H   H    99-100                      131   OH     H     Cl   H   H   Cl   H    H   H   114-115                      132   OH     H     H    Cl  H   Cl   H    H   H   97-98                        133   OH     Cl    H    Cl  H   Cl   H    H   H   78-79                        134   OH     Cl    H    Cl  Cl  Cl   H    H   H   123-124                      135   OH     H     Cl   Cl  H   Cl   H    H   H   109-110                      136   OH     Cl    H    Cl  H   H    H    H   H   94-95                        137   OH     Cl    H    Cl  Cl  H    H    H   H   168-169                      138   OH     Br    H    Br  H   H    H    H   H   121-122                      139   OH     Cl    H    Cl  Cl  H    CH.sub.3                                                                            H   H   175-176                      140   OH     Cl    H    Cl  Cl  H    Br   H   H   178-179                      141   OH     Br    H    Br  H   H    Br   H   H   135-136                      142   OH     H     H    Br  H   H    Cl   H   H   105-106                      143   OH     Br    H    Br  H   H    Cl   H   H   116-117                      144   H      H     OH   Cl  H   Cl   Cl   H   H   144-145                      145   H      Cl    OH   Cl  H   H    Cl   H   H   165-167                      146   H      Cl    OH   Cl  H   H    Cl   Cl  H   175-176                      147   H      Cl    OH   Cl  H   H    Br   H   H   159-160                      148   H      Cl    OH   H   Cl  H    Cl   Cl  H   147-148                      149   Cl     H     OH   H   H   Cl   Cl   H   H   159-160                      150   H      Cl    OH   H   H   H    Cl   Cl  H   121-122                      151   H      Cl    OH   Cl  H   H    H    H   H   144-145                      152   H      Cl    OH   Cl  H   Cl   Cl   H   H   162-163                      153   H      Cl    OH   Cl  H   CH.sub.3                                                                            H    H   H   158-159                      154   H      Cl    OH   Cl  H   Cl   H    H   H   139-140                      155   H      Cl    OH   H   Cl  Cl   H    H   H   176-177                      156   Cl     H     OH   H   Cl  H    Cl   Cl  H   197-198                      ______________________________________                                    

EXAMPLE 2

6.7 g 2-hydroxy-3,5,-d-trihlorophenylpropylketone were treated in a mixture of 10 ml water and 25 ml dioxane with 1.0 g sodium hydroxide to form the sodium salt. At 5° C 1.0 g of sodiumborohydride were then added and the reaction solution kept at 25° C for 5 hours with stirring. After this time the mixture was solidified with 2-N-hydrochloric acid and stirred for 1 further hour; from this the compound crystallized, precipitating first as an oil, of the formula ##STR11## fully. This was filtered off, washed with water, dried and recrystallised once from methylene chloride-hexane for purification; melting point 130°-131° C. The Pure yield amounts to 5.2 g.

In similar fashion the compounds given in the following table B can be prepared. The general formula for compounds of table B is:

                  TABLE B                                                          ______________________________________                                          ##STR12##                   (II)                                                                                       Melting                               Compound                                 point                                 No.      A             Z.sub.1                                                                              Z.sub.2                                                                            Z.sub.3                                                                            Z.sub.4                                                                            in ° C                         ______________________________________                                         200     CH.sub.3       Cl    H   Cl  H   55,5 - 56,5                           201     CH.sub.3       H     Cl  Cl  H   84 - 85                               202     CH.sub.3       Br    H   Br  H    82 - 83,5                            203     CH.sub.3       Cl    H   Cl  Cl  100 - 101                             204     CH.sub.3CH.sub.2                                                                              Br    H   Br  H   63 - 64                               205     CH.sub.3CH.sub.2CH.sub.2                                                                      Cl    H   Cl  H   45 -46                                206     CH.sub.3CH.sub.2CH.sub.2                                                                      Br    H   Br  H   60 - 61                               207     CH.sub.3CH.sub.2CH.sub.2                                                                      H     Cl  Cl  H   64,5 - 65,5                           208     CH.sub.3CH.sub.2 CH.sub.2                                                                     H     Cl  H   Cl  94 - 95                               209     CH.sub.3CH.sub.2CH.sub.2                                                                      Cl    H   Cl  Cl  130 - 131                             210     CH.sub.3(CH.sub.2).sub.5CH.sub.2                                                              Cl    H   Cl  H   48 - 49                               211     CH.sub.3       H     Cl  H   Cl  77,5 - 78,5                           212     CH.sub.3CH.sub.2                                                                              Cl    H   Cl  H   46 - 47                               213     CH.sub.3CH.sub.2                                                                              H     Cl  H   Cl  102 - 103                              214                                                                                    ##STR13##      Cl    H   Cl  H   54 - 55                              215     CH.sub.3(CH.sub.2).sub.2CH.sub.2                                                              Cl    H   Cl  H   49 - 50                               216     CH.sub.3(CH.sub.2).sub.2CH.sub.2                                                              Br    H   Br  H   66,5 - 67,5                           217     CH.sub.3(CH.sub.2).sub.2CH.sub.2                                                              H     Cl  Cl  H   69,5 - 70,5                           218     CH.sub.3(CH.sub.2).sub.2CH.sub.2                                                              H     Cl  H   Cl  77 - 78                               219     CH.sub.3(CH.sub.2).sub.2CH.sub.2                                                              Cl    H   Cl  Cl  108 -  109                            220     CH.sub.3(CH.sub.2).sub.3CH.sub.2                                                              Cl    H   Cl  H   Oil                                   221     CH.sub.3(CH.sub. 2).sub.3CH.sub.2                                                             Br    H   Br  H   64 - 65                               222     CH.sub.3(CH.sub.2).sub.3CH.sub.2                                                              H     Cl  H   Cl  64 - 65                               223     CH.sub.3(CH.sub.2).sub.3CH.sub.2                                                              Cl    H   Cl  Cl  66,5 - 67,5                           224     CH.sub.3(CH.sub.2).sub.4CH.sub.2                                                              Cl    H   Cl  H   Oil                                   225     CH.sub.3(CH.sub.2).sub.4CH.sub.2                                                              H     Cl  H   Cl  75,5 - 76,5                           226     CH.sub.3(CH.sub.2).sub.5CH.sub.2                                                              H     Cl  H   Cl  73 - 74                               ______________________________________                                    

EXAMPLE 3 Determination of the minimum inhibiting concentration (MIC) against bacteria and moulds by the gradient plates test Nos. 1) +2)++

Gradient test 1 is given by W. Szybalski et al., Science 116, 26 (1952).

Gradient plate test 2 is that given by Nuesch and Knuesel, "Sideromycins", in the book by Gottlieb and Shaw, "Antibiotics, Mechanism of Action", volume 1 (1967),Springer Verlag.

The compound of formulae 1 and 2 were mixed as suitable formulations (e.g. as solutions in dimethylsulfoxide) of given concentration with warm brain heart infusion-agar (bacteria) or mycophil-agar (moulds). The liquid mixtures were poured onto a solid wedge-shaped base agar layer and likewise allowed to solidify.

The test organism was then applied in a line perpendicular to the gradient with a pasteurpipetto. After incubation for 24 hours at 37° C (bacteria) or 72 hours at 30° C (moulds) the length of the bacteria which had grown on the inoculation line was measured and expressed in parts per million of active agent. The results are given in the following tables C to F.

                  TABLE C                                                          ______________________________________                                         Minimum inhibiting concentration against Staphylococcus                        aureus (Bacteriostasis).                                                       Compound                                                                               MIC in ppm   Compound    MIC in ppm                                    ______________________________________                                         100     8            115         0,4                                           101     30           116          2                                            102     3            117         10                                            103     2            118         0,2                                           104     20           119         0,4                                           105     3            120          4                                            106     3            121         0,1                                           107     0,5          122          3                                            108     0,5          123         0,3                                           109      0,25        124         0,3                                           110     3            125          4                                            111     1            126          4                                            112     2            127          3                                            113     0,3          128         20                                            114     0,5          129          3                                            130     3            145         50                                            131     30           146         20                                            132     50           147         25                                            133     10           148          6                                            134     3            149         20                                            135     9            150         20                                            136     30           152         25                                            137     3            154         30                                            138     10           155         30                                            139     3,5          156          4                                            140     2            201         35                                            141     2            203         20                                            142     30           204         60                                            143     2            205          3                                            144     20           206         0,3                                                          207       30                                                                   208        4                                                                   209        2                                                                   210       0,2                                                                  211       30                                                                   213       30                                                                   215       20                                                                   216       10                                                                   217       20                                                                   218        3                                                                   219        1                                                                   220        2                                                                   221       0,6                                                                  222       2                                                                    223       0,2                                                                  224        1                                                                   225        3                                                                   226       0,2                                                   ______________________________________                                    

                  TABLE D                                                          ______________________________________                                         Minimum inhibiting concentration against Escherichia                           coli (Bacteriostasis).                                                         Compound                                                                               MIC in ppm   Compound  MIC in ppm                                      ______________________________________                                         101     20           117       40                                              102     20           119       20                                              103     10           120       40                                              104     50           122       15                                              105     35           126       10                                              106     40           127       40                                              108     30           128       50                                              109     15           130       20                                              110     20           131       70                                              111     20           133       60                                              112     25           135       30                                              113     30           136       66                                              114     30           137       40                                              115     10           138       50                                              116     20           140       30                                                             141     20                                                                     142     40                                                                     143     30                                                                     149     50                                                                     150     45                                                                     154     50                                                                     156     50                                                                     201     50                                                                     203     40                                                                     205     40                                                                     206     35                                                                     207     40                                                                     208     30                                                                     209     30                                                                     213     30                                                                     215     40                                                                     216     20                                                                     217     20                                                                     218     10                                                                     222     10                                                      ______________________________________                                    

                  TABLE E                                                          ______________________________________                                         Minimum inhibiting concentration against Aspergillus                           niger (Fungistasis).                                                           Compound                                                                               MIC in ppm   Compound  MIC in ppm                                      ______________________________________                                         100     30           119       10                                              101     60           120       50                                              102     40           122       25                                              103     20           126       30                                              104     50           127       30                                              105     30           129       40                                              106     20           130       25                                              108     20           133       60                                              110     30           135       45                                              111     20           136       60                                              112     40           140       40                                              113     40           142       60                                              115     10           143       40                                              116     15           144       70                                              117     55           145       20                                                             148     15                                                                     149     40                                                                     150     40                                                                     152     55                                                                     156     20                                                                     203     30                                                                     206     80                                                                     207     90                                                                     208     40                                                                     209     10                                                                     213     40                                                                     215     70                                                                     216     50                                                                     217     50                                                                     218     20                                                                     219     10                                                                     220     60                                                                     221     30                                                                     222     20                                                      ______________________________________                                    

                  TABLE F                                                          ______________________________________                                         Minimum inhibiting concentration against Tricho-                               phyton mentagrophytes (Fungistasis).                                           Compound                                                                               MIC in ppm   Compound  MIC in ppm                                      ______________________________________                                         100     3            116       2                                               101     10           117       10                                              102     10           118       0,1                                             103     0,2          119       0,1                                             104     4            120       4                                               105     4            121       4                                               106     2            122       4                                               107     1            123       0,2                                             108     0,3          124       30                                              110     4            125       4                                               111     0,3          126       3                                               112     3            127       3                                               113     3            128       20                                              114     1            129       3                                               115     0,4          130       1                                               131     10           148       4                                               132     10           149       10                                              133     4            150       5                                               134     1            151       30                                              135     7            152       10                                              136     10           153       30                                              137     3            154       2                                               138     3            155       10                                              139     2            156       4                                               140     1            201       20                                              141     1            203       4                                               142     5            204       10                                              143     3            205       30                                              144     10           206       10                                              145     10           207       5                                                              208     2                                                                      209     2                                                                      210     0,4                                                                    212     0,5                                                                    213     5                                                                      215     20                                                                     216     4                                                                      217     10                                                                     218     0,4                                                                    219     0,3                                                                    220     20                                                                     221     0,1                                                                    222     0,4                                                                    223     2                                                                      224     3                                                                      225     1                                                                      226     10                                                      ______________________________________                                    

EXAMPLE 4

A specimen of 140 g cotton-poplin was impregnated at 20° C for 7 minutes in a bath of the following composition:

1000 ml water

2.7 ml cloth softening rinsing dye (containing 7% of a mixture of di-octadecyl and di-hexadecyl-dimethylammonium chloride).

15 mg of the compound of formula (109) (added as a solution in 0.5 ml dimethylsulfoxide)

The so treated cloth specimen was squeezed out after 100% dyebath take up and then dried at 45° C.

For testing the action against bacteria, roundels of 20 mm diameter were cut from the impregnated cloth and laid on brain-heart infusion agar plates, which had been pre-infected with Staphylococcus aureus. The plates were then incubated for 24 hours at 37° C.

Two observations were made, that of the zone of inhibition arising around the roundels (inhibition zone in mm) and the determinable growth (%) above or below the cloth. The inhibition zone was only a trace quantity while the determinable growth was 0%.

Similar effects were obtained with further compounds of formula 1 or 2.

EXAMPLE 5

For the manufacture of an anti-microbial tablet of soap, 2.4 g of one of the compounds of Formula 1 or 2 were added to the following mixture:

120 g natural soap in flake form

0.12 g disodium salt of ethylenediaminetetraacetic acid (dihydrate)

0.24 g titanium dioxide.

The soap shavings obtained by rolling were powdered with a high speed mixture and then pressed to soap tablet form.

Concentrated aqueous solutions of the anti-microbial soaps were mixed into warm brain heart infusion agar so that in-corporation dilution rose with 2, 10, 20, 100 etc. parts per million active agent were produced. The warm mixtures were poured into petri dishes, allowed to solidify and then infected with Staphylococcus aureus.

After 24 hour incubation at 37° C the minimum inhibiting concentration was determined. The results are shown in the following table. Similar results were obtained by the use of other compounds of formfulae 1 and `.

    ______________________________________                                                         Minimum inhibiting concentration                                               of the anti-microbial soap in                                  Compound No.    p.p.m. active agent                                            ______________________________________                                         104             -< 20                                                          105             -< 20                                                          106             -< 20                                                          108             -<  2                                                          109             -<  2                                                          ______________________________________                                    

EXAMPLE 6

Specimens of 100 g cotton-cretonne were impregnated on the foulard with 1% solutions of compounds of formula 1 in isopropanol at 20° C and then squeezed out with 100% bath take-up.

In the same way, samples of 100 g wool cheviot were treated.

The textiles which were dried at 30° to 40° C contained 1% by weight of active agent taken on their own weight.

For testing the action against bacteria, roundels of 10 mm diameter cut from the impregnated cloth, dewatered and watered, were laid for 24 hours at 29° C on brain heart infusion agar plates which had been previously infected with Staphylococcus aureus. The plates were then incubated for 18 hours at 37° C.

Two factors were observed: first, the inhibition zone (in mm) arising round the roundels and second, the microscopically determinable growth (in %) under or on the cloth.

Results are expressed in the following table; similar results were obtained also with further compounds of formulae 1 and 2

    ______________________________________                                                        unwatered watered                                                                    Inhib-        Inhib-                                      Substrate            ition         ition                                       (with 1%             zone    Growth                                                                               zone  Growth                                active agent)                                                                            Compound   (mm)    (%)   (mm)  (%)                                   ______________________________________                                                   103        8       0     9     0                                               108        5       0     4     0                                     Cotton    115        9       0     5     0                                               116        8       0     5     0                                               152        4       0     2     0                                               103        5       0     2     0                                               108        3       0     4     0                                     Wool      115        6       0     5     0                                               116        5       0     5     0                                               152        Trace   0     2     0                                     ______________________________________                                    

EXAMPLE 7 Substantivity tests with calf-hide roundels

Calf-hide roundels of 10 mm diameter were dipped for 2 minutes in 8% aqueous solutions of the anti-microbial soaps produced according to Example 4. After 3 minutes rinsing in flowing water, the roundels were laid on brain-heart infusion agar plates which had been pre-infected with Staphylococcus aureus. Finally the plates were incubated for 20 hours at 37° C.

The zone of inhibition arising around the calf-ride roundels was observed in mm and the microscopically determinable growth under or on the roundels was determined in %. Results are as follows:

    ______________________________________                                                        Inhibition zone in                                              Soap with Compound No.                                                                        mm             Growth in %                                      ______________________________________                                         105            1              0                                                109            1              0                                                ______________________________________                                    

Similar values were obtained using other compounds of formulae 1 and 2.

EXAMPLE 8

The following mixture was milled on the twin-roll mill at 150° C for 20 minutes:

100.00 g polyvinylchloride

19.20 g di-(2-elthyl-hexyl-phthalate)

27.00 g di(2-ethyl-hexyl-sebacate)

1.50 g Ba/Cd-laurate

0.25 g Stearic acid

7.80 g of a solution of 3.10 g of a compound of formula 1 in 4.70 g di(2-ethyl-hexyl-phthalate)

The roll separation was adjusted so that 1 mm thick sheets were formed which were then pressed for 20 minutes at 165°-170° C under a pressure of 1,400 kg/cm².

For testing the action against bacteria, discs of 10 mm diameter were stamped from the rolled soft polyvinylchloride sheet and laid on brain-heart infusion agar plates which had previously been infected with Staphyloccocus aureus. The plates were then incubated for 24 hours at 37° C.

The zone of inhibition arising round the discs was measured in mm and the microscopically determinable growth above and below the soft polyvinylchloride was measured in %.

The results are given in the following table: Similar action is observed with other compounds of formulae 1 and 2.

    ______________________________________                                                     Zone of Inhibition                                                 Compound No.                                                                               (mm)             Growth (%)                                        ______________________________________                                         106         Trace            0                                                 108         3                0                                                 115         2                0                                                 156         2                0                                                 ______________________________________                                     

We claim:
 1. A composition for combatting bacteria or fungi comprising (1) a fungicidally or bactericidally effective amount of a compound of the formula ##STR14## wherein each of X and X' is halogen, each of X₁ and X₂ is hydrogen or halogen, Alk is straight or branched chain alkyl having from 1 to 8 carbon atoms, and the hydroxy group is in the 2- or 4-position to the carbinol bridge, and (2) a carrier.
 2. The composition according to claim 1 wherein the hydroxyl group is in the 2-position to the carbinol bridge and Alk represents straight chain alkyl having from 3 to 7 carbon atoms.
 3. The composition according to claim 1 wherein X and X' are the same and are chlorine or bromine, X₁ and X₂ are hydrogen, and Alk is n-butyl or n-amyl.
 4. A method of combatting bacteria and fungi which comprises applying thereto a bactericidally or fungicidally effective amount of a compound according to claim
 1. 5. A method according to claim 4 wherein the hydroxyl group is in the 2-position to the carbinol bridge and Alk represents a straight chain alkyl having from 3 to 7 carbon atoms.
 6. The method according to claim 5 in which the compound ##STR15##
 7. The method according to claim 4 wherein X and X' are the same and are chlorine or bromine, X₁ and X₂ are hydrogen, and Alk is n-butyl or n-amyl.
 8. The method according to claim 7 in which the compound ##STR16##
 9. The method according to claim 7 in which the compound ##STR17##
 10. The method according to claim 7 in which the compound ##STR18## 